Oxygenated aliphatic compounds derived from 2-ethylbutyraldehyde



Patented July 27, 1937 OXYGllNATED ALIPHATIC COMPOUNDS DE- RIVED FROM z-nrnrmo'rrnamnnrns Jacob N. Wickcrt, Charleston, and Clare A. Carter, South Charleston, W. Va., assignors, by

mesne assignments, to Union Carbide and Carbon Corporation, a corporation of New York o Drawing.-

Application December Serial No. 758,032

I 17 Claims. (0152 0-134) The invention relates wine production of certain new oxygenated compounds derived from 2-ethylbutyraldehyde, and-more especially it concerns the production ofa new series of ketones and their derivatives," including saturated S601 ondary branched-chain alcohols and sulphate esters thereof. These ketones as a classpossess properties adapting them for use as lacquer solvents, particularly forum with natural resins and with synthetic resins used' for brushing fin- I ishes, such as those oi the vinyl, polyvinyl, and

'glyptal types. "The secondary alcohols andthe sulphate esters-thereof possess in high degree properies adapting them for use as wetting, foaming, emulsifying and impregnating agents, as

detergents, and in treatment liquors in the textile,

leather and other industries.

In its broadest scopethe'invention involves the condensation of ethylbutyraldehyde with an aliphatic-ketone to form a ketol which then is made to lose the elements of water to form an unsaturated ketone. The latter may be hydrogenated selectively to a saturated ketone or still: further to the,corresponding secondary'alcohol. More over, the above-mentioned unsaturated and saturated' ketones thus formed may be condensed further with a primary or a secondary aldehyde, such as butyraldehyde or ethylhexaldehyde, and the ketol dehydrated to form an unsaturated ketone which then may be hydrogenated as hereinafter described to-produce the corresponding secondary alcohol;

The secondary alcohol, upon sulphation under suitable conditions, yields an acid sulphate ester of. the alcohol which, upon neutralization with a suitable base, forms the corresponding neutral sulphate ester. Among bases suitable for the purpose may be mentioned alkaline compounds of the alkali metals and or the alkaline earth metals, and nitrogenous bases such as ammonia, the alkyl amines, and substituted amines such as triethanolamine. v

The condensation of ethylbutyraldehyde with the selected ketone may be eflected at tempera-- tures of 20 to 30 C.,'in the presence 01' any alkali which ,will catalyze the reaction, such as caustic soda, potash, or some organic amine such as, diethanol'amine, pyridine, etc.-

A concurrent reaction, due to direct oxidation or to the auto-oxidation and'reduction oi. the

aldehyde, which is catalyzed by the alkali, (Canj nizzaros reaction), and. which renders the reaction mixtures acid, is minimized or prevented by I the use of starting materials and equipment free from copper, manganese, and other metals known to catalyze the air-oxidation of these. aldehydes, and by avoiding the presence 01 air in the reaction vessel. High yields of the ketols may be secured and acid formation-minimized also bythe intermittent} or slow addition of the alkali, in small amounts during the condensationso as to maintain a minimum alkalinity consistent with suitable operation. Preferably the reaction mixture is kept just alkaline to phenolphthalein at all imes. The resultant ketols easily lose the. elements oil water, especially upon heating above .C. in thepresence of acatalytic proportion (less than 1%, usually .1 to' .2% by weight) of a dehydrate ing agent such as sulphuric, phosphoric, or hydrobromic acids,'or a few crystals of iodine For those substances whose unsaturatedketones tend strongly to condense with themselves, a weak acid such as acetic, carbonic, or tartaric acid preferably is i use The resulting unsaturated ketones are quitestable to light and heat, but tend to condense with themselves to'form resins or tars in the presence of strong alkalies or acids. "The tendency of the lower" unsaturated ketones to vpolymerize may be reduced by using iodine as the dehydration catalyst.

The hydrogenation oithe unsaturated ketone. preferably is effected by molecular hydrogen in. to 10%--of an active hythe presence of from 1% drogenation catalyst, at, temperatures ranging from 60 to C. or more. However, the hydrogenation may be accomplished by any of the usual methods. Activated nickel catalysts such as those prepared from nickel-silicon, or nickelaluminum alloys are particularly suitable as catalysts, as are finely-divided platinum, and copper.

The hydrogenation may be effected at pressures rangingfrom atmospheric to around 1000 pounds per square inch, depending upon the desired degree of hydrogenation. urated ketone is the desired product, pressures of around 800 pounds per square inch and temperatures of about 60 to--'75 C. may be employed, aided by externalcooling of the reaction vessel.

Where a sat:

Where complete hydrogenation to the secondary alcohol is desired, the pressure I preferably may be around 900 pounds per square inch, and a temperature slowly rising to a maximum of 150 C. may be used. The hydrogenation products is illtered, and the filtrate, usually water white, is fractionated, preferably under reduced pressure.

The alkyl sulphates 01' these secondary alcohols may be made by known sulphation methods,

of these products was-measured by the method of relative drop numbers. This method consists in dropping slowly at fixed volume of a 25% aqueous solution of the sulphate ester from a ground tip into a body of kerosene at 30 C. The tip is calibrated by counting the number of drops of pure Water formed under like conditions; and the greater number of drops, of the solution being examined measuresthe relative interfacial tension or emulsifying power of the substancetested. When this measurement is made carefully from a tip of known diameter, the interfacial tension can be calculated indynes', as described by Hare kins 8: Brown, J. A. C. S., 41, 499 (1919); and E. B. Millard, Ind. Eng. Chem., 15, '810 (1923).

' The invention may be illustrated by the following examples, in'which thereactantsare given in parts by weight:

Example 1 To a cooled and agitated mixture of 1550 parts of acetone and 1700 parts of 2-ethylbutyraldehyde was added enough of a 10% solution of sodium hydroxide in methanolto render the mixture just alkaline to phenolphthalein. The temperature which rose quickly to 60 C. was reduced by cooling to 30 C. which was maintained during the reaction period of twenty hours. Small additions of caustic soda totalling 15 g. were made at intervals to maintain the desired degree of alkallnity.

The reaction mixture was then neutralized by acetic acid (carbonic, tartaric, or other weak acid may be used), and the neutral. liquid was filtered to remove the salt formed. The clear filtrate was fractionally distilled. The low-boiling fractions, consisting of unreacted starting materials, methe anol and some water, were removed under atmos pheric pressure. After this stripping operation, a small proportion (about 1 c. c. per 5 liters) of concentrated sulphuric acid was added as dehydration catalyst.

case, upon distillation of the said filtrate the hereinafter described intermediate ketol, evidently 3,ethylheptanol-4-one-6; is obtained, boiling at about 87 C. at 3 mm. of mercury absolute pres sure, and boiling at about 205-206 C. with some decomposition at atmospheric pressure.

The fraction of the acidified filtrate boiling principally at 7' 7-78,C. under 13 mm. of mercury,

product was cooled, filtered, and the filtrate-frac- Y tionally distilled, yielding the saturated ketone,

The fractionation was then continued under reduced pressure.

This addition of acid may be omitted, in which 3,ethylheptone-6, a water-white liquid having considerable solvent power for vinyl resins and other synthetic resins and materials used in lacquer production, and which was compatible with the usual lacquer solvents and diluents.

' Separate portions of thesaturated and of the unsaturated 9-carbon ketone mentioned above were subjected to hydrogenation in the following manner, yielding the same secondary alcohol.

The selected ketone was mixed with 5% of its weight ofv active .nickel catalyst and was heated to 150 C. with agitation for from twelve to eighteen hours, under a hydrogen pressure of from 700 to 900 pounds per square inch. The resultant product was filtered; and the filtrate was fractionally distilled under reduced pressure, yielding the secondary nonyl alcohol, 3,ethylheptanol6, as a colorless liquid, boiling at about 100 C. at 27 mm. of mercury absolute pressure.

This secondary nonyl alcohol was dissolved in an equal weight ,oipp' dichlorethyl, ether, and this was slowly mixed at about 10 C. with a solution of one partof chlorsulphonic'acid in three parts of 8 3 dichlorethyl ether, with constant agitation while passing air through the liquid. (The air can be replaced by nitrogen, natural gas, or other gas, inert to the reactants under the reaction conditions. This gas removes most of the hydrogen chlorideformed.) The final reaction product was then poured into cold water andneutralized with sodium hydroxide, thus forming the sodiumsalt of the mono-alkyl sulphate of the alcohol. This salt was extracted from the ether solution with water; and the ether layer was decanted. A small amount of sodium bicarbonate, (less than 1% of the contained solids) was:

added to the aqueoussolution, and it was evaporated to dryness under reducedpressure at a temperature below 100 C. The residue was ex:- tracted with methanol to dissolve the sulphate ester and separate it from inorganic salts, and the mixture-was filtered. The clear filtrate was then evaporated to dryness, yielding the sodium nonyl sulphateas a snow-white wax, which was completelysoluble in water, methanol, and other organic solvents. Other characteristics of this compound are contained in the accompanying Table II.

Example 2 A mixture of 920 parts'of acetone and 2300 parts of Z-ethylbutyraldehyde was condensed by addition of 12 parts of caustic soda. dissolved in methanol, in the manner describedin Example 1. The reaction product wasstripped of unreacted starting materials, acidified with sulphuric acid, and was fractionated under reduced pressure as in Example 1. I

After separation of the 9 -carbon unsaturated ketone fraction mentioned in Example 1, and a later mid-cut, a fraction was obtained boiling principally at about l56-160 C. under 15 mm. of mercury absolute pressure. This was a 15- carbon doubly unsaturated ketone, apparently l 3,9, diethylundecadien-4,7,-one 6, formed by the condensation of a second molecule of ethylbutyraldehyde with the Q carbon ketol or withthe 9-carbon unsaturated ketone, followed by a dehydration.

\ Portions of this 15-carbon doubly unsaturated ketone were hydrogenated" in the manner described in Example 1, one portion at temperatures around 6070 C., and another portion at temperatures ranging up to 150 C. That at'the lower temperatures yielded the saturated ketone,

apparently 3,9,diethylundecanone-6; while the high temperature hydrogenation yielded thesec ondary pentadecyl alcohol, 3,9-d1ethylundecanol- 6, recovered as shown in Example 1.

The-corresponding sodium pentadecyl sulphate was prepared in the same manneras the sodium nonyl sulphate described in Example 1". It yields a stable froth when shaken inwater. solution; and shows important detergent properties.

The unsaturated Q-carbon ketone mentioned in Example 1 may be substituted forthe acetone as a starting materiaL -condensing with ethylbutyraldehyde to form theabove-mentioned 15- carbon doubly-unsaturated ketone, with overall yields of more than of the latter.

Likewise, by reacting ethylbutyraldehyde. with the saturated 9-carbon .ketone produced in Example 1, in the presence ofcaustic alkali dissolved in methanol, there is produced a singly unsaturated ketone, 3,9-diethylundecen-4-one 6, which by hydrogenation in the manner described in Example 1 may be converted into the respective saturated 15-carbon ketoneand into the secondary pentadecyl alcohol described above.

Furthermore, the unsaturated 9-carbon ketoneprepared in Example l'may be condensed further with an aldehyde to produce a new series of compounds. ketone was'condensed with 1.55 parts of ethylhexaldehyde. ,The reaction was catalyzed with" .045; part of sodium hydroxide under the conditions described in Example 1. The Ill-carbon doubly unsaturated ketone 3,9 diethyltridecadien- 4- 7-one-6, described hereinafter in Example 5; was produced.

By substituting in the above example the saturated 9-carbon ketone of Example 1 for the unsaturated 'Q-carbon ketone, and following the same procedure, there is produced an unsaturated l'l-carbon ketone, 3,9 diethyltridecen-7-one-6,

with an efilciency of around 89% on the basis of the ethylhexaldehyde used.

Example 3 i Over a period of four hours, 11 mols 1.1 kg.) of 2-ethylbutyraldehyde was slowly added to a mixture containing 20 mols (2kg); of methylisoe butyl ketone and a methanolic solution containing'20 g. ofpotassium hydroxide,- maintained at a temperature of 15 tofl25 C. during this period and for 16 hours thereafter. The reaction mixture was made just neutral to phenolphthalein by glacial acetic acid, and was filtered. A crystal of iodine was added to the clear filtrate, and it was {fractionally distilled. After removal of the unreacted starting materials, the pressure was reduced to 10 mm. ofmercury absolute, and the. product was obtained boiling at 98 to' 100 C.. at this pressure. This unsaturated 12-carbon'. "ketone apparently was 3,ethyl-8-methylnonene- '4-one-6.

The latter was hydrogenated in, the liquid phase at temperatures up to C. under 700- 900 pounds per square inch hydrogen pressure,

usinga nickel catalyst, until no further hydrogen absorption occurred. The cooled product was filtered, and the filtrate fractionally distilled under reduced pressure.

For example, 1.7 parts of the said ethylundecanol-6. It

yellow liquid were recovered, boiling between and C. under! mm. of mercury absolute 1 this hydrogenation, a quantity of the saturated The fraction boil- I ing at 108-1l 0 C. under 7 mm. of mercury abester! of the alcohol as a colorless wax. The methylisobutyl ketone used in this example may be prepared by hydrogenating mesityl .oxide, (obtained by condensing acetone ,with itseli' in the presence of an alkali), and dehydrating the (ii-,-

acetone alcoholthus formed.

-, I Example} I i v I 12 mols of z-ethylbutyraldehyde and 25 mols of methylamyl ktona-the latter of which may be 10 cordance with the conditions of Example 1. After 15 nineteen hours the product was washed with about half itsvolumeqof water, the insoluble layer was decanted from of! the wash water, and was made slightly acid to phenolphthalein with phosphoric acid. The acidified liquid was fractionallydistilled under reduced pressure, and the unsaturated 13-carbonketone, apparently 3 ethylundecen-4-one-6, was recovered as a pale yellow liquid boiling at 138 C.at .19 mm. of mercury absolute pressure.

This unsaturated ketone was hydrogenated under 700-900 poundsper square inch gauge pressure at 150 C., in thepresence of an active nickel catalyst. .The product was filtered. and the filtrate was fractionallydistilledin vacuum to. give the secondary tridecyl alcohol as a'waterwhite liquid-boiling at 142 C. at 18 mm. of mercury. absolute pressure. This apparently was 3; V was sulphated with chlorsulphonic acid in the manner set out in Example 1, forming the acid sulphate ester which,

-uponfineutralization in the manner therein de scribed, yielded the corresponding sodium tridecyl sulphate as a colorless wax, completely soluble in water and organic solvents.

Example 5 900 parts'of 2-ethylbutyraldehyde were added slowly during two hours to 2070 parts of unsaturated ll-carbon ketone, 5 ethylnonene-3- one-2, madev alkaline by 25 parts of KOH as a 10% methanolic solution, the temperature being maintained at v20-25 C. for twentyhours until the specific gravity at 20. C. jreacheda maximum- The product was made slightly acid to phenolphthalein with" sulphuric acid, and the mixture was filtered. The clear filtrate was distilled under reduced pressure. vAfter removal of the unreacted starting materials, 1005 parts of a pressure. This was the 17-carbon doubly unsaturated ketone, having apparently the formula 3,9." diethyltridecadien-4-7-one-6.

A portion'of-thi's ketone was hydrogenated undertheconditions set out in Example 1 in connection with the production of the saturated Q-carbon ketone. Upon fractional distillation of the filtrate obtained by filtering the product of I l-carbon ketone, apparently 3,9 diethyltrldecanone-G, was recovered, boiling at 162. C. under- 10 mm. of mercury absolute, and having the properties hereinafter set out. p v

Upon hydrogenating another portion of the unsaturated ketone under'pressures of 700-900 pounds per square inch, and at temperatures up to around 150 C., the secondaryheptadecylalcohol, 3,9 dlethyltridecanol-6 was formed, boiling at sure.

It was recovered upon fractional distillation at reduced pressure of the filtrate secured upon filtration of this hydrogenated product.

Upon sulphating this alcohol with a solution of supra. Practical qualitative wetting tests were made by dropping loose balls of cotton and wool yarn on the surface of '75 c.c.of 25% aqueous solutions of the sulphate esters contained in c. c.

chlorsulphonic acid in flfidichlorethyl ether, in beakers held at 26 C., and noting the time elapsed accordance with the conditions of Example 1, before the yarn sank to the bottom of each beaker. and neutralizing the acid sulphate ester with Those sulphates having 13 or more carbon atoms caustic soda, the sodium heptadecyl sulphate was in the molecules wet cotton at least six y times as produced as a colorless wax having excellent wetrap y.a Wet W at least twenty t es ting and cleansing properties. rapidly,-as those having less than 13 carbon Exam 1e 6 atoms in the molecules. p By the practice of the invention it is possible 2 parts of the saturated ll-carbon ketone, 5, V toproduce, in operations under commercially atethylnonanone-2, was condensed with 1.2 parts tainable conditions, a series of ketols, ketones and of 2-ethylbutyraldehyde, using .02 part of secondary alcohols having more than 8 carbon caustic soda dissolved in methanol, following the toms in h ir molecules. nd lso the dium or procedure outlined in Example 1. Upon fracoth r wa eru l secondary lk l phate tional distillation of the crude product from the derived fr m s c alcohols, h h omp n dehydration step, and redistillation of the fracpossess imp r n properties p ng m f r a tion boiling between and 165 C. under 4 wide variety of uses in the textile, leather, lacquer mm. of mercury absolute pressure, the mono unand other industries. The process of the invensaturated l'I-carbon ketone, 3,9 diethyltridecention involves the employment as starting mate- 4-one-6, was obtained. This ketone boils at 142 rial of compounds readily produced commerunder 3 of mercury absolute D cially; and a succession of steps are used in which Up n hydrogenation of Portions 9 131118 Product; the conditions. of temperature and pressure are in accordance with two procedures of so selected that undesirable destructive decompog s i respect-Age fi z g i g sition of the starting materials and intermediate Table I sets out some-of the physical properi gb ties of certain members of the series of ketones secon, er a c0 0 S 0 e and secondary alcohols of the present invention; non are aptlvely-dlssolved by usual Organic and Table 11 lists identifying properties of cersolvents Such as methanol d ethanol, acetonfe' tain of the sodium secondary alkyl sulphates of benzol, toluol; hexane, chloroform and ethyl dithe invention. chloride.

i TABLE I Physical properties of condensation products Carbon Boiling range atoms Speciilc Refractiv Item in s f gra vi y m ex 760 mm. m r fi r;

- vacuum C. 1 3, ethylheptanol-4-one-6 9 206 87l3 mm 0.928 1.4462 2 3,ethylhepten-4-one-6 9 192 77-8/13 0.848 1.4479 3 3, ethylheptanone-G 9 86 72/11 0.837 1.4263 4 3, ethylheptanol-fi 9 9 100/27 0.837 1.4351 5 3,9diethylundecodienel,7-one-6 15 234 158/ 0. 7 .47 9 6 3,9diethylundecanone-finr 15 281 143/9 0.854 1.4453 7 3, Qdiethylundecanol-G 15 283 158/17 0.854 1.4492 8 3, ethyl-B-methylnoneneA-one 12 100/l0 0. 844 9 3,ethyl-8 methy1n0nanol-6 12 232 109/? I 0.834 1.4390 10 3,ethylundecen-4-one-6--." 13 256 138/19 -8 1-4552 11 3, ethylundecanol-fi 13 258 142/18 0.839 1.4455 12 3, 9 diethyltridccadien-4, 7- one-6 17 313 -160/7 O. 865 1. 4750 13 3, 9 diethyltridecanone-6 17 306 162/10 -8 7 14 3.9diethyltridecanol-6 17 308 134/3 0.847 1.4537 1s 3,9diethyltridecen-4-one-6 17 309 142 3 0. 850 1.4640 1s 3,9diethyltrideceu-7-one-6 17 30s 146/3 0.855 1.4598

TABLEII The invention is susceptible, of modification within the scope of the appended'claims. We claim- 0.25 eouss Inn 11 1 7 0 1. The process of producing a saturated alit H i 1 phatic oxygenated compound having more than Substance Drop 2 2 3;? eight carbon atoms in the molecule, which com nusrg liig at dyiies prisescondensing ethylbutyraldehyde with an all I 5%.; phatic ketone in the presence of an alkali, removing the elements of water from the resultant ketol sodium-Bowl Sulfate 30 32 9 to form an unsaturated ketone havingin its mole- Sodium dodecyl sulr t 42 2 cule six more carbon atoms than are in the first- 32 2:3 named ketone, and partially hydrogenating the sodium'heptgdecylsulfate 6 unsaturated ketone to at least remove the un- Watel' 22 t r t bond i The relative drop numbers and interfacial tenslon values were obtained by the method of Harkins and Brown, and that of Millard, mentioned 2. The process of producing a saturated ali-' phatic ketone having more than eight carbon atoms in the molecule, which comprises con densing 2-ethylbutyraldehyde with a ketone selected from the group consisting of acetone,

methylamyl ketone; methylisobutyl ketone, 5,

ethylnonene 3 one 2, 5,ethylnonanone 2, 3, ethylheptenei-one-fi, and 3,ethylheptanone-6, in the presence of an alkali, removing the elements of water from the resultant ketolto form an. unsaturated ketone having in its molecule six more carbon atoms than in the first-named ketone, and partially hydrogenating the unsaturated ketone to remove the unsaturated bond.

3. The process which comprises condensing ethylbutyraldehyde with an aliphatic ketone in the presence of an alkali, removing the elements of water from the ketol thus formed, thereby pro I ducing an unsaturated ketone, and hydrogenating the latter under superatmospheric pressure at temperatures up to about 150 C. in thepresence 1 of an active hydrogenating catalyst..

'4. As a chemical compound, an aliphatic saturated-ketone in the form of a clear liquid boiling at a temperature above about 186 C. under atmospheric. pressure and having. the composition represented by the formula wherein R designates. analiphatic residue.

5. As a chemical compound, a saturated nonyl ketone, the same being a liquid boiling at 72 C.

sure, and boiling at 281 C. under atmospheric pressure, having a specific gravity at 20 C. of

.854, and apparently having the composition indicated by the designation 3,9 diethylundecanone-6.

7. As a chemical compound, diethyltridecanone, the same being a 17-carbon saturated aliphatic ketone boiling at about 162 C. under 10 mm. of mercury. absolute pressure, and boiling at about 306 C. under atmospheric pressure.

8. As a newchemical compound, a secondary aliphatic branched-chain alcohol having the structure corresponding to the designation wherein R represents a straight-chain or a branched-chain aliphatic radical.

- 9. A chemical compound identical with that resulting from the hydrogenation of an unsaturated Q-carbon ketone, the same being a secondary branched-chain nonyl alcohol in the form of a clear liquid boiling at 100C. under 27 mm. of mercury absolute pressure, and boiling at 191 C. under atmospheric pressure.

10. A chemical compound identical with that resulting from the hydrogenation of a doublyunsaturated 15-carbon ketone, the same being a secondary branched-chain'pentadecyl alcohol in the form of a clear liquid boiling at 158 C. under 17 mm. of mercury'absolute pressure, and boiling at 283 C. under atmospheric pressure.

11. A chemical compound identical with that resulting from the hydrogenation of .an unsaturated 1'7-carbon ketone, the same being a secondary branched-chain heptadecyl alcohol in .the form of a clear liquid boiling at 134 C. under 3 mm. of mercury absolute pressure, and

boiling at 308 C. under atmospheric pressure.

12. The process of producing a saturated secondary branched-chain monohydrlc alcohol having more than eight carbon atoms in the molecule, which comprises condensing 2-ethylbutyraldehyde with a ketone selected from the group thereof consisting of acetone, methylamyl ketone, methylisobutyl ketone, 5 ethylnonene-3- one-2, 5 ethylnonanone-Z, 3 ethylheptene-i-one- 6, and 3 ethylheptanone-6, in the presence of an alkali,.removing the elements of water from the resultant ketol to form an unsaturated ketone having in its molecule six more carbon atoms than the first-named ketone hydrogenating the unsaturated ketone under superatmosphericf pressure at temperatures within a range up to around 150 C., .and recovering from the resultant reaction 'mixture the saturated secondary branched-chain monohydric alcohol thus produced.

13. The process which comprises condensing 2-ethylbutyraldehyde with a ketone. selected from the group consisting of acetone, methylamyl ketone, methylisobutyl ketone, 5,ethylnonene-3- one-2, 5,ethylnonanone-2, 3,ethylheptene-4-one- 6 and 3,ethylheptanone-6, in the presence of an alkali,'removing the elements of water from'the resultant ketol to form an unsaturated ketone having in its molecule six more carbon atoms than the first-named ketone, and at least partially hydrogenating the said unsaturated ketone.

14. Process of producing a saturated aliphatic oxygenated compound which comprises condens ing 2-ethylbutyraldehyde with an aliphaticketone in the presence of a small amount of an alkali, maintaining a selectedlow alkalinity in the reaction mixture during the condensation by the comprise condensing 2-ethylbutyraldehyde with an aliphatic ketone in the presence of a small amount of an alkali, while minimizing acid formation by the gradual addition of the alkali in amounts adapted to maintain in the reaction mixture a low alkalinity, removing the elements of water from the resultant ketol, thereby-forming an unsaturated ketone, and hydrogenating the unsaturated ketone.

16. As a chemical compound, a saturated aliphatic oxygenated compound, the same being a liquid having a structure corresponding to the designation RR'iCHz) 2CH(C2H5) 021 15 wherein R represents an alkyl group, and R represents a group selected from the class consisting of a. carbonyl group and a secondary alcohol group.

1'7. As a chemical compound, a saturated aliphatic ketone, the same being a high-boiling liquid having the composition represented by the formula 1 I wherein R designates a radical selected from the group thereof consisting of methyl, ethylamy, and ethylnonyl radicals.

JACOB N. WICKERT. -CLARE A. CARTER.

CERTIFICATE OF CORRECTION.

Patent No. 2,088,017. July 27, 1937.

JACOB N. WICKERT, ET AL.

It is hereby certified'that error appears in the printed specification 7 of the above numbered patent requiring correction as follows: Page 2, second column, line 1, for "3,rethy lheptone-6" read 3, ethylheptanone-S;

and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office. I Y

Signed and sealed this 21st day of September, A. D; 1937.

Henry Van Arsdale (Seal) f v Acting Commissioner of Patents. 

